JP6370371B2 - NATAO3: LA2O3 catalyst with cocatalyst composition for photocatalytic reduction of carbon dioxide - Google Patents
NATAO3: LA2O3 catalyst with cocatalyst composition for photocatalytic reduction of carbon dioxide Download PDFInfo
- Publication number
- JP6370371B2 JP6370371B2 JP2016520805A JP2016520805A JP6370371B2 JP 6370371 B2 JP6370371 B2 JP 6370371B2 JP 2016520805 A JP2016520805 A JP 2016520805A JP 2016520805 A JP2016520805 A JP 2016520805A JP 6370371 B2 JP6370371 B2 JP 6370371B2
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- Prior art keywords
- natao
- catalyst composition
- catalyst
- cocatalyst
- carbon dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims description 142
- 239000000203 mixture Substances 0.000 title claims description 100
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 52
- 230000009467 reduction Effects 0.000 title claims description 27
- 239000001569 carbon dioxide Substances 0.000 title claims description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 26
- 230000001699 photocatalysis Effects 0.000 title claims description 22
- 238000000034 method Methods 0.000 claims description 60
- 229930195733 hydrocarbon Natural products 0.000 claims description 50
- 150000002430 hydrocarbons Chemical class 0.000 claims description 49
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
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- 229910019899 RuO Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910002845 Pt–Ni Inorganic materials 0.000 claims description 3
- 229910018883 Pt—Cu Inorganic materials 0.000 claims description 3
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- 230000005670 electromagnetic radiation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- 239000002585 base Substances 0.000 description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
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- 238000006243 chemical reaction Methods 0.000 description 17
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- 230000004913 activation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
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- 150000002815 nickel Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002265 electronic spectrum Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003256 NaTaO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 description 1
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6486—Tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
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Description
ここに記載される主題は、二酸化炭素の光触媒還元のための触媒組成物および触媒組成物の調製方法に概して関する。特に、本開示は、水の存在下での二酸化炭素の光触媒還元によって低級炭化水素および炭化水素オキシジェネートを製造するための、タンタル酸ナトリウム、改質剤、および少なくとも1つの共触媒を含む触媒組成物に関する。 The subject matter described herein generally relates to a catalyst composition for photocatalytic reduction of carbon dioxide and a method for preparing the catalyst composition. In particular, the present disclosure relates to a catalyst comprising sodium tantalate, a modifier, and at least one cocatalyst for producing lower hydrocarbons and hydrocarbon oxygenates by photocatalytic reduction of carbon dioxide in the presence of water. Relates to the composition.
代替資源および再生可能資源に対する国際的な取り組みにも関わらず、従来の化石燃料、すなわち原油、ガスおよび石炭は、主なエネルギー源であり続けている。二酸化炭素(CO2)は、化石燃料が燃焼されるとき、放出されるガスの1つである。CO2は、地球大気内に熱を閉じ込めるが、窒素酸化物、メタン、およびフッ化ガスほど温室効果ガス(GHG)としての影響が強いわけではない。しかしながら、化石燃料の継続的な使用が、過去数十年にわたって、大気CO2濃度の大幅な増加をもたらしている。CO2放出量の増加が地球全体の温暖化に関係することから、これは非常に懸念されることである。したがって、CO2の低減が、地球全体の温暖化を阻止するための重要な課題である。 Despite international efforts on alternative and renewable resources, traditional fossil fuels, namely crude oil, gas and coal, continue to be the main energy sources. Carbon dioxide (CO 2 ) is one of the gases released when fossil fuels are burned. CO 2 traps heat in the Earth's atmosphere, but is not as strong as a greenhouse gas (GHG) as nitrogen oxides, methane, and fluorinated gases. However, continued use of fossil fuels has resulted in significant increases in atmospheric CO 2 concentration over the past decades. This is a great concern because the increase in CO 2 emissions is related to global warming. Therefore, the reduction of CO 2 is an important issue for preventing global warming.
豊富なCO2を捕え、かつ利用するために有効な技術を開発するために、世界中で取り組みが行われている。CO2を高エネルギーを含有するまたは付加価値を有する燃料/化学品に変換することまたは再生すること(化学的炭素削減としても知られる)は、現在世界中で注目されている魅力的な手段である。様々なCO2変換方法が調査されており、これには化学的手段、光化学的手段、生物化学的手段、生物−光化学的手段、放射化学的手段、電子化学的手段、電子−光化学的手段、生物−光−電子化学的手段が含まれる(Scibioh et al.,Proc.Indn.Natl.Acad.Sci.,2004,70 A(3),407)。 Efforts are being made around the world to develop technologies that are effective in capturing and utilizing abundant CO 2 . Converting or regenerating CO 2 into high energy or value-added fuels / chemicals (also known as chemical carbon reduction) is an attractive means currently attracting worldwide attention is there. Various CO 2 conversion methods have been investigated, including chemical means, photochemical means, biochemical means, bio-photochemical means, radiochemical means, electrochemical means, electro-photochemical means, Bio-photo-electrochemical means are included (Scibioh et al., Proc. Indn. Natl. Acad. Sci., 2004, 70 A (3), 407).
外部の水素源を用いる、CO2の、ギ酸、メタノール、メタンなどの化学品への従来法による触媒還元が実施可能である(Nam et al.,Appl.Catalysis A.Gen.,1999,179,155)。しかしながら、CO2の触媒還元のための従来法は費用がかかる。CO2還元を経済的にかつ持続可能なものとするために、水素の製造は持続可能な方法を通じて行われなくてはならない。 Catalytic reduction of CO 2 to chemicals such as formic acid, methanol, methane, etc. using an external hydrogen source can be carried out by conventional methods (Nam et al., Appl. Catalysis A. Gen., 1999, 179, 155). However, conventional methods for catalytic reduction of CO 2 are expensive. In order to make CO 2 reduction economical and sustainable, hydrogen production must be carried out through sustainable methods.
三井化学株式会社(日本)は、非常に活性が高い触媒配合物、CO2(石油化学プラントから放出された)および光触媒水分解により得られた水素を用いたメタノール合成法を開発した(http://www.mitsui.chem.co.jp.e.dt,2008年8月にアクセス)。しかしながら、光触媒法または光電子触媒(PEC)法による水素の大量生産は、始まったばかりである。 Mitsui Chemicals, Inc. (Japan) has developed a methanol synthesis method using a highly active catalyst formulation, CO 2 (released from a petrochemical plant) and hydrogen obtained by photocatalytic water splitting (http: // accessed at www.mitsui.chem.co.jp.e.dt, August 2008). However, mass production of hydrogen by photocatalytic or photoelectrocatalytic (PEC) processes has only just begun.
チタニア触媒、改質チタニア触媒、層状チタニア触媒、および多くの他の混合酸化物触媒が、CO2の光触媒還元に使用されてきた(Mori et al.,RSC Advances,2012,2,3165)。特開昭54−112813号公報は、ドナーとしてペリレンまたはトリフェニルアミンを用い、アクセプターとしてベンソキノンのような電子吸引基を有する芳香族炭化水素を用いた、CO2のギ酸への光化学還元方法を開示している。NiOを担持した、ランタンドープNaTaO3が、UV放射の下で、水を化学両論的量の水素および酸素に分解するための光触媒として使用されてきた(Kudo et al.,J.Am.Chem.Soc,2003,125,3082)。 Titania catalysts, modified titania catalysts, layered titania catalysts, and many other mixed oxide catalysts have been used for photocatalytic reduction of CO 2 (Mori et al., RSC Advances, 2012, 2, 3165). JP 54-1112813 discloses a photochemical reduction method of CO 2 to formic acid using perylene or triphenylamine as a donor and an aromatic hydrocarbon having an electron-withdrawing group such as benzoquinone as an acceptor. doing. Lanthanum-doped NaTaO 3 supported on NiO has been used as a photocatalyst to decompose water into stoichiometric amounts of hydrogen and oxygen under UV radiation (Kudo et al., J. Am. Chem. Soc, 2003, 125, 3082).
アルカリ金属タンタル酸が、水素の存在下での二酸化炭素の還元のための光触媒として使用されてきており、生成物として一酸化炭素を与える。タンタル酸カリウムの光触媒活性は、アルカリ金属タンタル酸の中で最も高かった(Tanaka et al.,Applied Catalysis B:Environmental,2010,96,565)。NaTaO3系触媒内で光励起された電子の動力学が、時間分解赤外分光法によって調べられた。LaドープNaTaO3内で励起された電子は、効率的な水への電子移動を仲介する共触媒(NiO)に移動した(Yamakata et al.,J.Phys.Chem.B,2003,107,14383)。 Alkali metal tantalate has been used as a photocatalyst for the reduction of carbon dioxide in the presence of hydrogen, giving carbon monoxide as the product. The photocatalytic activity of potassium tantalate was the highest among the alkali metal tantalates (Tanaka et al., Applied Catalysis B: Environmental, 2010, 96, 565). The dynamics of the photoexcited electrons in the NaTaO 3 based catalyst were investigated by time-resolved infrared spectroscopy. Electrons excited in La-doped NaTaO 3 transferred to a cocatalyst (NiO) that mediates efficient electron transfer to water (Yamakata et al., J. Phys. Chem. B, 2003, 107, 14383). ).
CO2は非常に安定な分子であり、したがってその活性化および変換はエネルギーを大量に消費する過程である。光および/または電子化学活性化により補助された、活性化手順、触媒/バイオ工程の組み合わせが、所望の変換を実現するために必要とされる。同様に難しいのは、水素を産出するための水の還元/分解であり、活性化段階の同様の組み合わせを必要とする。 CO 2 is a very stable molecule, so its activation and conversion is a process that consumes large amounts of energy. Activation procedures, catalyst / bioprocess combinations, assisted by light and / or electrochemical activation, are required to achieve the desired conversion. Equally difficult is the reduction / cracking of water to produce hydrogen, which requires a similar combination of activation steps.
ここに記載される主題は、ベース触媒としてのタンタル酸ナトリウム(NaTaO3)、ベース触媒に対して0.5から5重量%(%w/w)の範囲の改質剤、およびベース触媒に対して0.05から5重量%(%w/w)の範囲の量の少なくとも1つの共触媒を含む触媒組成物に関する。 The subject matter described herein is sodium tantalate (NaTaO 3 ) as the base catalyst, a modifier in the range of 0.5 to 5 wt% (% w / w) relative to the base catalyst, and the base catalyst. And at least one cocatalyst in an amount ranging from 0.05 to 5% by weight (% w / w).
本開示の他の態様は、触媒の製造方法を提供し、この方法は以下の段階を含む:La2O3/NaTaO3を得るために、120〜200℃の温度範囲で、4〜24時間、熱水条件下、水性媒体中で、五酸化タンタル(Ta2O5)、三酸化ランタン、およびNaOHの混合物を加熱する段階、および触媒組成物を得るために、共触媒の少なくとも1つの塩でLa2O3/NaTaO3を含浸する段階。 Another aspect of the present disclosure provides a process for the preparation of a catalyst comprising the following steps: 4-24 hours at a temperature range of 120-200 ° C. to obtain La 2 O 3 / NaTaO 3. Heating a mixture of tantalum pentoxide (Ta 2 O 5 ), lanthanum trioxide, and NaOH in an aqueous medium under hydrothermal conditions, and at least one salt of the cocatalyst to obtain a catalyst composition Impregnating with La 2 O 3 / NaTaO 3 .
本開示のさらに他の態様は、低級炭化水素および炭化水素オキシジェネートの製造方法を提供し、この方法は以下の段階を含む:第1の混合物を得るために、反応器中で撹拌しながらNaOH水溶液に触媒組成物を懸濁させる段階、8〜12の範囲のpHを有する第2の混合物を得るために、第1の混合物に二酸化炭素を通過させる段階、および低級炭化水素および炭化水素オキシジェネートを製造するために、第2の混合物を300〜700nmの波長を有する電磁放射に曝す段階。 Yet another aspect of the present disclosure provides a process for producing lower hydrocarbons and hydrocarbon oxygenates, which process comprises the following steps: with stirring in a reactor to obtain a first mixture Suspending the catalyst composition in aqueous NaOH, passing carbon dioxide through the first mixture to obtain a second mixture having a pH in the range of 8-12, and lower hydrocarbons and hydrocarbon oxy Exposing the second mixture to electromagnetic radiation having a wavelength of from 300 to 700 nm to produce a jenate.
本願主題のこれらのおよび他の特徴、態様、および利点は、以下の記載および添付される請求項を参照してよく理解されるだろう。この概要は、単純化した形態で様々な概念を紹介するために提供される。この概要は、請求項に係る主題の重要な特徴または必須の特徴を特定することを意図しておらず、請求項に係る主題の範囲を制限するために使用されることを意図しない。 These and other features, aspects and advantages of the present subject matter will be better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.
添付の図面と関連して詳細な説明が記載される。図面において、参照番号の最も左の桁はその参照番号が最初に現れた図面を示す。同様の特徴および構成要素を参照するために図面全体で同じ番号が使用される。 The detailed description is described with reference to the accompanying figures. In the drawings, the leftmost digit of a reference number indicates the drawing in which the reference number first appears. The same numbers are used throughout the drawings to reference like features and components.
ここで任意のブロック図は、本願の主題の原理を具現化する説明的な方式の概念的な表示であることが当業者には理解されるだろう。 It will be appreciated by those skilled in the art that any block diagram is a conceptual representation of an illustrative scheme embodying the principles of the present subject matter.
本発明は、これ以降さらに完全に記載される。実際のところ、本発明は多くの異なる形態で具現化されてよく、ここに説明される実施形態に制限されると解釈されるべきではない。むしろ、これらの実施形態は、この開示が適切な法的要件を満たすように提供される。明細書において、および添付される請求項において使用されるとき、文脈から明らかに規定されていない限り、単数形の「a」、「an」、「the」は、複数の指示対象を含む。 The invention will be described more fully hereinafter. Indeed, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; Rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in the specification and in the appended claims, the singular forms “a”, “an”, “the” include plural referents unless the context clearly dictates otherwise.
ここに記載される主題は、二酸化炭素の光触媒還元のための触媒組成物に関する。本開示の主題は、ベース触媒としてタンタル酸ナトリウム(NaTaO3)、改質剤、および少なくとも1つの共触媒を含む触媒組成物を提供することである。触媒組成物中の金属は、元素の形態で、または金属酸化物として、または金属塩として、またはそれらの混合物として存在してよい。 The subject matter described herein relates to a catalyst composition for the photocatalytic reduction of carbon dioxide. The subject of this disclosure is to provide a catalyst composition comprising sodium tantalate (NaTaO 3 ) as a base catalyst, a modifier, and at least one cocatalyst. The metal in the catalyst composition may be present in elemental form or as a metal oxide or as a metal salt or as a mixture thereof.
本開示の実施形態は、ベース触媒としてタンタル酸ナトリウム(NaTaO3)、ベース触媒の0.5から5重量%の範囲の改質剤、およびベース触媒の0.05から5重量%の範囲の量の少なくとも1つの共触媒、を含む触媒組成物に関する。 Embodiments of the present disclosure include sodium tantalate (NaTaO 3 ) as a base catalyst, a modifier in the range of 0.5 to 5% by weight of the base catalyst, and an amount in the range of 0.05 to 5% by weight of the base catalyst. At least one cocatalyst.
本開示の他の実施形態は、改質剤が、三酸化ランタン(La2O3)、La(ランタン)およびこれらの混合物からなる群から選択される触媒組成物を提供する。本開示の他の実施形態は、改質剤が三酸化ランタン(La2O3)である触媒組成物を提供する。 Other embodiments of the present disclosure provide a catalyst composition wherein the modifier is selected from the group consisting of lanthanum trioxide (La 2 O 3 ), La (lanthanum), and mixtures thereof. Another embodiment of the present disclosure provides a catalyst composition in which the modifier is lanthanum trioxide (La 2 O 3 ).
本開示のさらに他の実施形態は、改質剤がNaTaO3上に含浸され、La2O3/NaTaO3を形成する、触媒組成物を提供する。改質剤(La2O3)は、熱水法により、ベース触媒(NaTaO3)上に、固定され、または堆積され、または含浸される。La2O3/NaTaO3の他の表し方は、La:NaTaO3である。
Yet another embodiment of the present disclosure, the modifying agent is impregnated on NaTaO 3, to form a La 2 O 3 /
本開示は、ベース触媒としてタンタル酸ナトリウム(NaTaO3)、ベース触媒の1から3重量%の範囲の改質剤、およびベース触媒の0.05から2重量%の範囲の量の少なくとも1つの共触媒、を含む触媒組成物に関する。 The present disclosure relates to at least one co-agent of sodium tantalate (NaTaO 3 ) as a base catalyst, a modifier in the range of 1 to 3% by weight of the base catalyst, and an amount in the range of 0.05 to 2% by weight of the base catalyst. A catalyst composition comprising a catalyst.
本開示は、La2O3/NaTaO3上に共触媒が含浸された触媒組成物にさらに関する。共触媒は、La2O3/NaTaO3上に、固定され、または堆積され、または含浸される。本開示の他の実施形態において、共触媒が、Pt、Ag、Au、RuO2、CuO、NiO、およびそれらの混合物を含む群から選択される触媒組成物を提供する。本開示のさらに他の実施形態において、共触媒が、Pt、Ag、Au、Ru、Cu、Ni、およびそれらの混合物を含む群から選択される触媒組成物を提供する。触媒組成物中の共触媒は、元素の形態で、または金属酸化物として、またはそれらの混合物として存在してよい。共触媒の重量%は、ベース触媒に対するものであり、共触媒の元素形態に基づくものである。本開示は、Au/La2O3/NaTaO3、Ag/La2O3/NaTaO3、RuO2/La2O3/NaTaO3、Pt/La2O3/NaTaO3、CuO/La2O3/NaTaO3、NiO/La2O3/NaTaO3、Pt/Ni/La2O3/NaTaO3、およびPt/Cu/La2O3/NaTaO3を含む群から選択される触媒組成物も提供する。 The present disclosure further relates to a catalyst composition impregnated with a cocatalyst on La 2 O 3 / NaTaO 3 . The cocatalyst is fixed, deposited or impregnated on La 2 O 3 / NaTaO 3 . In other embodiments of the present disclosure, the co-catalyst provides a catalyst composition selected from the group comprising Pt, Ag, Au, RuO 2 , CuO, NiO, and mixtures thereof. In yet another embodiment of the present disclosure, a catalyst composition is provided wherein the cocatalyst is selected from the group comprising Pt, Ag, Au, Ru, Cu, Ni, and mixtures thereof. The cocatalyst in the catalyst composition may be present in elemental form or as a metal oxide or as a mixture thereof. The weight percent of the cocatalyst is relative to the base catalyst and is based on the elemental form of the cocatalyst. The present disclosure includes Au / La 2 O 3 / NaTaO 3 , Ag / La 2 O 3 / NaTaO 3 , RuO 2 / La 2 O 3 / NaTaO 3 , Pt / La 2 O 3 / NaTaO 3 , CuO / La 2 O Also a catalyst composition selected from the group comprising 3 / NaTaO 3 , NiO / La 2 O 3 / NaTaO 3 , Pt / Ni / La 2 O 3 / NaTaO 3 , and Pt / Cu / La 2 O 3 / NaTaO 3 provide.
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、Au(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示のさらに他の実施形態において、触媒組成物が提供され、当該触媒組成物は、1重量%Au(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provide a catalyst composition, which is Au (0.05-2 wt% with respect to the base catalyst) / La 2 O 3 / NaTaO 3 . In yet another embodiment of the present disclosure, a catalyst composition is provided, wherein the catalyst composition is 1 wt% Au (based on the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示はさらなる触媒組成物を提供し、当該触媒組成物は、Ag(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示のさらなる実施形態において、触媒組成物が提供され、当該触媒組成物は、1重量%Ag(ベース触媒に対して)/La2O3/NaTaO3である。 The present disclosure provides a further catalyst composition, which is Ag (0.05-2 wt% with respect to the base catalyst) / La 2 O 3 / NaTaO 3 . In a further embodiment of the present disclosure, a catalyst composition is provided, wherein the catalyst composition is 1 wt% Ag (relative to the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、RuO2(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示はさらに触媒組成物を提供し、当該触媒組成物は、1重量%RuO2(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provide a catalyst composition, which is RuO 2 (0.05-2 wt% relative to the base catalyst) / La 2 O 3 / NaTaO 3 . The present disclosure further provides a catalyst composition, which is 1 wt% RuO 2 (relative to the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、Pt(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示は触媒組成物を提供し、当該触媒組成物は、0.15重量%Pt(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provide a catalyst composition, which is Pt (0.05-2 wt% with respect to the base catalyst) / La 2 O 3 / NaTaO 3 . The present disclosure provides a catalyst composition, which is 0.15 wt% Pt (relative to the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示は触媒組成物を提供し、当該触媒組成物は、CuO(ベース触媒に対して1−3重量%)/La2O3/NaTaO3である。本開示のさらなる実施形態において、触媒組成物が提供され、当該触媒組成物は、1重量%CuO(ベース触媒に対して)/La2O3/NaTaO3である。 The present disclosure provides a catalyst composition, which is CuO (1-3 wt% relative to the base catalyst) / La 2 O 3 / NaTaO 3 . In a further embodiment of the present disclosure, a catalyst composition is provided, wherein the catalyst composition is 1 wt% CuO (relative to the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、NiO(ベース触媒に対して0.1−0.5重量%)/La2O3/NaTaO3である。本開示は触媒組成物をさらに提供し、当該触媒組成物は、0.2重量%NiO(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provides a catalyst composition, said catalyst composition, (0.1-0.5 wt% with respect to the base catalyst) NiO is / La 2 O 3 / NaTaO 3 . The present disclosure further provides a catalyst composition, wherein the catalyst composition is 0.2 wt% NiO (relative to the base catalyst) / La 2 O 3 / NaTaO 3 .
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、Pt(ベース触媒に対して0.05−2重量%)/Ni(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示のさらに他の実施形態において、触媒組成物が提供され、当該触媒組成物は、0.15重量%Pt(ベース触媒に対して)/0.2重量%Ni(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provide a catalyst composition, the catalyst composition comprising Pt (0.05-2 wt% with respect to the base catalyst) / Ni (0.05-2 with respect to the base catalyst). % By weight) / La 2 O 3 / NaTaO 3 . In yet another embodiment of the present disclosure, a catalyst composition is provided, the catalyst composition being 0.15 wt% Pt (based on the base catalyst) /0.2 wt% Ni (based on the base catalyst). / La 2 O 3 / NaTaO 3 .
本開示の他の実施形態は、触媒組成物を提供し、当該触媒組成物は、Pt(ベース触媒に対して0.05−2重量%)/Cu(ベース触媒に対して0.05−2重量%)/La2O3/NaTaO3である。本開示は触媒組成物を提供し、当該触媒組成物は、0.15重量%Pt(ベース触媒に対して)/1.0重量%Cu(ベース触媒に対して)/La2O3/NaTaO3である。 Other embodiments of the present disclosure provide a catalyst composition, the catalyst composition comprising Pt (0.05-2 wt% with respect to the base catalyst) / Cu (0.05-2 with respect to the base catalyst). % By weight) / La 2 O 3 / NaTaO 3 . The present disclosure provides a catalyst composition, which is 0.15 wt% Pt (based on the base catalyst) /1.0 wt% Cu (based on the base catalyst) / La 2 O 3 / NaTaO. 3 .
本開示のさらに他の実施形態において触媒組成物が提供され、当該触媒組成物は、ベース触媒に対して0.05−1.0重量%のPt、ベース触媒に対して0.05−2.0重量%のNi、およびLa2O3/NaTaO3;およびベース触媒に対して0.05−1.0重量%のPt、ベース触媒に対して0.05−2.0重量%のCu、およびLa2O3/NaTaO3、を含む群から選択される。
In yet another embodiment of the present disclosure, a catalyst composition is provided, the catalyst composition being 0.05-1.0 wt% Pt relative to the base catalyst, 0.05-2. 0 wt% of Ni, and La 2 O 3 /
本開示の主題は、低級炭化水素および炭化水素オキシジェネートを製造するための、アルカリ性の水の存在下での、二酸化炭素の光触媒還元に関する。本開示は触媒組成物に関し、この触媒組成物は、低級炭化水素および炭化水素オキシジェネートを製造するための、アルカリ性の水の存在下での、二酸化炭素の光触媒還元に用いられる。 The subject of the present disclosure relates to the photocatalytic reduction of carbon dioxide in the presence of alkaline water to produce lower hydrocarbons and hydrocarbon oxygenates. The present disclosure relates to a catalyst composition, which is used for photocatalytic reduction of carbon dioxide in the presence of alkaline water to produce lower hydrocarbons and hydrocarbon oxygenates.
本開示は、触媒組成物の製造方法にさらに関し、この方法は、La2O3/NaTaO3を得るために、120〜200℃の温度範囲で、4〜24時間、熱水条件下、水性媒体中で、五酸化タンタル(Ta2O5)、三酸化ランタン、およびNaOHの混合物を加熱する段階、および触媒組成物を得るために、共触媒の少なくとも1つの塩でLa2O3/NaTaO3を含浸する段階、を含む。 The present disclosure further relates to a method for producing a catalyst composition, which is aqueous under a hydrothermal condition for 4-24 hours at a temperature range of 120-200 ° C. to obtain La 2 O 3 / NaTaO 3. Heating a mixture of tantalum pentoxide (Ta 2 O 5 ), lanthanum trioxide, and NaOH in the medium, and at least one salt of the cocatalyst to obtain a catalyst composition, La 2 O 3 / NaTaO 3 impregnating.
本開示の実施形態は方法に関し、La2O3/NaTaO3は濾過され、含浸の前に4から20時間、80〜120℃で乾燥される。本開示の他の実施形態は方法に関し、含浸の後に80〜120℃で4〜20時間乾燥される。 Embodiments of the present disclosure relate to a method wherein La 2 O 3 / NaTaO 3 is filtered and dried at 80-120 ° C. for 4 to 20 hours prior to impregnation. Another embodiment of the present disclosure relates to a method wherein the impregnation is dried at 80-120 ° C. for 4-20 hours.
本開示の他の実施形態は方法を提供し、乾燥の後、任意に、100から500℃の温度範囲で5から10時間水素の流入により還元が行われる。本開示は方法に関し、乾燥の後、任意に、200から500℃の温度範囲で2から24時間焼成が行われる。 Other embodiments of the present disclosure provide a method, wherein after drying, the reduction is performed by flowing hydrogen, optionally in the temperature range of 100 to 500 ° C. for 5 to 10 hours. The present disclosure relates to a method wherein, after drying, calcination is optionally performed at a temperature range of 200 to 500 ° C. for 2 to 24 hours.
本開示の実施形態は方法に関し、共触媒の塩は、Ni(NO3)2.6H2O、H2PtCl6、HAuCl4、Ag(NO3)2、Cu(NO3)2.6H2O、およびRuCl3.XH2Oを含む群から選択される。 Embodiments of the present disclosure relate to methods wherein the cocatalyst salt is Ni (NO 3 ) 2 . 6H 2 O, H 2 PtCl 6 , HAuCl 4 , Ag (NO 3 ) 2 , Cu (NO 3 ) 2 . 6H 2 O, and RuCl 3 . Selected from the group comprising XH 2 O.
本開示の銅塩は、硝酸銅、塩化銅、および酢酸銅を含む群から選択される。銅塩は、単純に銅を含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、銅塩はCu(NO3)2・6H2Oである。 The copper salt of the present disclosure is selected from the group comprising copper nitrate, copper chloride, and copper acetate. The copper salt may be any organic or inorganic metal salt that simply comprises copper. Embodiments of the present disclosure relate to a method wherein the copper salt is Cu (NO 3 ) 2 .6H 2 O.
本開示は方法にさらに関し、白金塩が、酢酸白金、塩化白金、および硝酸白金を含む群から選択される。白金塩は、単純に白金を含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、白金塩はH2PtCl6である。 The present disclosure further relates to a method wherein the platinum salt is selected from the group comprising platinum acetate, platinum chloride, and platinum nitrate. The platinum salt may simply be any organic or inorganic metal salt containing platinum. An embodiment of the present disclosure relates to a method wherein the platinum salt is H 2 PtCl 6 .
本開示の銀塩は、硝酸銀、塩化銀、および酢酸銀を含む群から選択される。銀塩は、単純に銀を含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、銀塩はAg(NO3)2である。 The silver salt of the present disclosure is selected from the group comprising silver nitrate, silver chloride, and silver acetate. The silver salt may simply be any organic or inorganic metal salt containing silver. An embodiment of the present disclosure relates to a method wherein the silver salt is Ag (NO 3 ) 2 .
本開示は方法に関し、ニッケル塩が、硝酸ニッケル、塩化ニッケル、および酢酸ニッケルを含む群から選択される。ニッケル塩は、単純にニッケルを含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、ニッケル塩はNi(NO3)2・6H2Oである。 The present disclosure relates to a method wherein the nickel salt is selected from the group comprising nickel nitrate, nickel chloride, and nickel acetate. The nickel salt may simply be any organic or inorganic metal salt containing nickel. Embodiments of the present disclosure are directed to a method wherein the nickel salt is Ni (NO 3 ) 2 .6H 2 O.
本開示は方法にさらに関し、ルテニウム塩が、酢酸ルテニウム、塩化ルテニウム、および硝酸ルテニウムを含む群から選択される。ルテニウム塩は、単純にルテニウムを含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、ルテニウム塩はRuCl3XH2Oである。 The present disclosure further relates to a method, wherein the ruthenium salt is selected from the group comprising ruthenium acetate, ruthenium chloride, and ruthenium nitrate. The ruthenium salt may simply be any organic or inorganic metal salt containing ruthenium. Embodiments of the present disclosure are directed to a method wherein the ruthenium salt is RuCl 3 XH 2 O.
本開示の金塩は、硝酸金、塩化金、および酢酸金を含む群から選択される。金塩は、単純に金を含む任意の有機または無機金属塩であってよい。本開示の実施形態は方法に関し、金塩はHAuCl4である。 The gold salt of the present disclosure is selected from the group comprising gold nitrate, gold chloride, and gold acetate. The gold salt may be any organic or inorganic metal salt that simply comprises gold. Embodiments of the present disclosure relate to a method wherein the gold salt is HAuCl 4 .
本開示は方法にさらに関し、水は蒸留され、脱イオン化される。好ましくは非イオン性である、任意の他の精製された形態の水を使用することもできる。 The present disclosure further relates to a method wherein water is distilled and deionized. Any other purified form of water, which is preferably nonionic, can also be used.
本開示は、低級炭化水素および炭化水素オキシジェネートを製造する方法にさらに関し、この方法は以下の段階を含む:第1の混合物を得るために、反応器中で撹拌しながら触媒組成物をNaOH水溶液に懸濁させる段階、8〜12の範囲のpHを有する第2の混合物を得るために、第1の混合物に二酸化炭素を通過させる段階、および低級炭化水素および炭化水素オキシジェネートを製造するために、第2の混合物を300〜700nmの波長を有する電磁放射に曝す段階。 The present disclosure further relates to a process for producing lower hydrocarbons and hydrocarbon oxygenates, the process comprising the following steps: to obtain a first mixture, the catalyst composition is stirred with stirring in a reactor. Suspending in aqueous NaOH, passing carbon dioxide through the first mixture to obtain a second mixture having a pH in the range of 8-12, and producing lower hydrocarbons and hydrocarbon oxygenates In order to expose the second mixture to electromagnetic radiation having a wavelength of 300-700 nm.
本開示において使用される反応器は、触媒懸濁液を照射するための石英窓を備えた、全ガラス温度自動調節光触媒反応器である。 The reactor used in the present disclosure is an all-glass temperature self-regulating photocatalytic reactor with a quartz window for irradiating the catalyst suspension.
本開示の実施形態は方法に関し、二酸化炭素ガスは純粋であり、使用前に乾燥される。二酸化炭素は、好ましくは、炭化水素および水分のトラップを通過することによって精製される。本開示は方法を記述し、第2の混合物は、20〜40℃の温度範囲で0.1から20時間照射に曝される。本開示は方法にさらに関し、第2の混合物は、周囲条件の下で照射に曝される。 Embodiments of the present disclosure relate to a method wherein the carbon dioxide gas is pure and is dried prior to use. The carbon dioxide is preferably purified by passing through a hydrocarbon and moisture trap. The present disclosure describes a method wherein the second mixture is exposed to irradiation in the temperature range of 20-40 ° C. for 0.1-20 hours. The present disclosure further relates to a method, wherein the second mixture is exposed to radiation under ambient conditions.
本開示の他の実施形態は方法を提供し、この方法において、低級炭化水素は、メタン、エタン、およびそれらの混合物を含む群から選択される。本開示の他の実施形態において、炭化水素オキシジェネートは、メタノール、エタノール、アセトアルデヒド、およびそれらの混合物を含む群から選択される。本開示は、二酸化炭素を、水との反応によって、低分子炭化水素およびアルコールおよびアルデヒドを含む炭化水素オキシジェネートの混合物に光触媒的に変換する方法に関する。本開示は、メタン、メタノール、エタン、エタノール、アセトン、ホルムアルデヒド、および遊離水素を含むがこれらに制限されない、低分子炭化水素および炭化水素オキシジェネートを製造する方法にさらに関する。 Other embodiments of the present disclosure provide a method, wherein the lower hydrocarbon is selected from the group comprising methane, ethane, and mixtures thereof. In other embodiments of the present disclosure, the hydrocarbon oxygenate is selected from the group comprising methanol, ethanol, acetaldehyde, and mixtures thereof. The present disclosure relates to a method of photocatalytically converting carbon dioxide to a mixture of low molecular weight hydrocarbons and hydrocarbon oxygenates including alcohols and aldehydes by reaction with water. The present disclosure further relates to methods of producing low molecular weight hydrocarbons and hydrocarbon oxygenates, including but not limited to methane, methanol, ethane, ethanol, acetone, formaldehyde, and free hydrogen.
本開示のさらに他の実施形態は方法に関し、この方法において、触媒組成物は、数ある炭化水素オキシジェネートおよび低分子炭化水素の中でも選択的にメタノールを製造するために、アルカリ性の水の存在下での二酸化炭素の光触媒還元に使用される。 Yet another embodiment of the present disclosure relates to a method in which the catalyst composition is present in the presence of alkaline water to selectively produce methanol among a number of hydrocarbon oxygenates and low molecular hydrocarbons. Used for photocatalytic reduction of carbon dioxide underneath.
本開示の他の実施形態は方法に関し、この方法において、水は二酸化炭素の光触媒還元のための水素源である。本開示は、二酸化炭素を低分子炭化水素および炭化水素オキシジェネートの混合物に光触媒的に転換するために、可視光からのフォトンがエネルギー源として、および水が水素(H2)源として使用される方法にも関する。 Another embodiment of the disclosure relates to a method, wherein water is a hydrogen source for the photocatalytic reduction of carbon dioxide. The present disclosure uses photons from visible light as an energy source and water as a hydrogen (H 2 ) source to photocatalytically convert carbon dioxide to a mixture of low molecular weight hydrocarbons and hydrocarbon oxygenates. It also relates to the method.
本開示は方法に関し、この方法において、触媒組成物は、分散媒体の照射のための石英窓を備えた被覆された全ガラス反応器内部で、アルカリ水溶液中にスラリー状態で分散される。本開示は方法にさらに関し、この方法において、触媒組成物はアルカリ溶液に分散され、溶解されたCO2の光還元を促進するために可視光で照射される前にCO2で飽和される。本開示は方法に関し、この方法において、アルカリ溶液は二酸化炭素の溶解度を高める。本開示のさらに他の実施形態は方法に関し、この方法において、二酸化炭素の濃度が高いことによって低級炭化水素および炭化水素オキシジェネートの収率が高まる。 The present disclosure relates to a method in which the catalyst composition is dispersed in slurry in an aqueous alkaline solution within a coated all glass reactor with a quartz window for irradiation of the dispersion medium. The present disclosure further relates to a method, in this method, the catalyst composition is dispersed in an alkaline solution, saturated with CO 2 before being irradiated with visible light in order to promote the photoreduction of dissolved CO 2. The present disclosure relates to a method in which an alkaline solution increases the solubility of carbon dioxide. Yet another embodiment of the present disclosure relates to a method, wherein a high concentration of carbon dioxide increases the yield of lower hydrocarbons and hydrocarbon oxygenates.
本開示の他の実施形態は方法に関し、光源は300〜700nmの範囲の波長を有し、光の紫外領域及び可視領域の双方を包含する250W Hgランプである。 Another embodiment of the disclosure relates to a method, wherein the light source is a 250 W Hg lamp having a wavelength in the range of 300-700 nm and encompassing both the ultraviolet and visible regions of light.
本開示の実施形態は、周囲温度及び大気圧において、二酸化炭素の光触媒還元により、二酸化炭素から低分子炭化水素および炭化水素オキシジェネートを製造する方法に関する。構造特性および光物理特性に関して調製され特徴付けられた触媒化合物は、一連の有用な炭化水素および炭化水素オキシジェネートを生産するために、水を用いたCO2の光還元に対して有意のかつ安定した活性を示した。このように、NaTaO3系触媒は、CO2光還元のための潜在的に有効な候補として有望である。CO2の光還元活性が、水の光触媒分解のための活性と密接に関連することが観察される。水の分解に対して最も高い活性を有するNiO−La:NaTaO3もまた、CO2の光還元に対して最大の活性を示す。ATaO3(AはLi、Na、K)触媒が、CO2の光還元に関して調べられているが、この方法は水素ガスの外部からの供給に基づいており、還元はCOのみに限定される。 Embodiments of the present disclosure relate to a method for producing low molecular weight hydrocarbons and hydrocarbon oxygenates from carbon dioxide by photocatalytic reduction of carbon dioxide at ambient temperature and atmospheric pressure. Catalyst compounds prepared and characterized with respect to structural and photophysical properties are significant and useful for photoreduction of CO 2 with water to produce a series of useful hydrocarbons and hydrocarbon oxygenates. It showed stable activity. Thus, NaTaO 3 based catalysts are promising as potentially effective candidates for CO 2 photoreduction. It is observed that the photoreduction activity of CO 2 is closely related to the activity for photocatalytic degradation of water. NiO-La: NaTaO 3, which has the highest activity for water decomposition, also exhibits maximum activity for photoreduction of CO 2 . An ATaO 3 (A is Li, Na, K) catalyst has been investigated for CO 2 photoreduction, but this method is based on the external supply of hydrogen gas and the reduction is limited to CO only.
本開示において、水素は、水の光触媒分解/酸化によりインサイチュで生成され、一連の炭化水素が形成される。主生成物としてのメタノールおよびエタノールでNaTaO3系触媒が例外的に安定な活性を示すことが観察される。Pt、Ag、Au、およびRuO2は、光生成された電子の有効なトラップとして働き、結果的に電荷キャリアの再結合の最小化を助け、La:NaTaO3の光吸収端を拡張し、これがCO2変換の改善をもたらす。他方で、NiOおよびCuOなどの酸化物が結合された半導体の役割を果たす。それらの伝導体エネルギーレベルが、図8において考えられるようにNaTaO3の伝導帯からの電子の容易な移動に適し、有効な電荷分離および活性の増加をもたらすためである。 In the present disclosure, hydrogen is generated in situ by photocatalytic decomposition / oxidation of water to form a series of hydrocarbons. It is observed that NaTaO 3 based catalysts show exceptionally stable activity with methanol and ethanol as main products. Pt, Ag, Au, and RuO 2 act as effective traps for the photogenerated electrons, thus helping minimize charge carrier recombination and extending the light absorption edge of La: NaTaO 3 , which results in an improvement of the CO 2 conversion. On the other hand, it functions as a semiconductor in which oxides such as NiO and CuO are combined. This is because their conductor energy levels are suitable for easy transfer of electrons from the conduction band of NaTaO 3 as considered in FIG. 8, resulting in effective charge separation and increased activity.
本発明の主題が、その特定の好ましい実施形態と関連して詳細を考慮しつつ記載されてきたが、他の実施形態が可能である。故に、添付される請求項の精神および範囲が、ここに含まれる好ましい実施形態の記載に限定されるべきではない。本発明の部分を構成する触媒組成物が、実施例の形態で以下に与えられる。 Although the subject matter of the present invention has been described in detail in connection with certain preferred embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred embodiments contained herein. The catalyst composition constituting part of the present invention is given below in the form of examples.
ここで本開示は実施例で説明され、これは本開示の働きを説明することを意図し、本開示の範囲に対してどのような限定も制限的に示すことを意図していない。別段の規定がない限り、ここで使用される全ての技術的なおよび科学的な用語は、本開示が属する当業者に通常理解されるものと同じ意味を有する。ここに開示されるものと同様のまたは等価の方法および材料が、開示される方法および組成物の実施に使用され得るが、例示的方法、装置、および材料がここに記載される。 The present disclosure is now described by way of example, which is intended to illustrate the workings of the present disclosure and is not intended to limit the scope of the present disclosure in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those disclosed herein can be used in the practice of the disclosed methods and compositions, exemplary methods, devices, and materials are now described.
実施例1
光触媒反応
NaTaO3系触媒複合物のCO2光還元法は、スラリー相において、バッチモードで実施された。図1に示される光源のための石英窓(2)(直径5cm)を備えた全ガラス温度自動調節光触媒反応器(1)が、水によるCO2光触媒還元を検討するために使用された。光の紫外および可視領域の双方(300〜700nm)を含む250WのHgランプ源(1)が使用された。触媒0.5gが、CO2の安定性を高めるために、かつ正孔スカベンジャーとして働くために、0.2MのNaOH水溶液500mlに分散された。触媒は、マグネチックスターラー(3)を用いた連続撹拌により懸濁状態に保たれた。(炭化水素および水分のトラップを通過することによって精製された)純粋かつ乾燥したCO2ガスで、酸素を除去するために30分間バブリングされた。アルカリ水溶液がCO2で完全に飽和されたとき、媒体のpHは13から8まで減少した。これらの条件の下で、媒体中で使用可能なCO2は、70,000μmolであると見積もられた。反応器入口(10)および出口(7)は、水と接触しているトラップされたCO2ガスで緊密に閉じられた。バッチモードにおける光化学反応が、照射を開始することによって始められた。気体および液体のサンプルが規則正しい間隔で収集されGCによって分析された。反応は20時間実施された。反応媒体の温度は、ジャケット中に水(4,6)を循環させることによって25℃に保持された。全てのタイプの炭化水素および炭化水素オキシジェネートの形成に消費されたCO2の量は、GC分析によって測定された。したがって、CO2の変換は、化学量論に基づいて計算された。
Example 1
Photocatalytic Reaction The CO 2 photoreduction method of NaTaO 3 based catalyst composite was performed in batch mode in the slurry phase. An all-glass temperature self-regulating photocatalytic reactor (1) with a quartz window (2) (5 cm diameter) for the light source shown in FIG. 1 was used to study CO 2 photocatalytic reduction with water. A 250 W Hg lamp source (1) containing both the ultraviolet and visible regions of light (300-700 nm) was used. 0.5 g of catalyst was dispersed in 500 ml of 0.2 M aqueous NaOH to increase CO 2 stability and to act as a hole scavenger. The catalyst was kept in suspension by continuous stirring using a magnetic stirrer (3). Pure and dry CO 2 gas (purified by passing through a hydrocarbon and moisture trap) was bubbled for 30 minutes to remove oxygen. When the aqueous alkali is completely saturated with CO 2, pH of the medium was reduced from 13 to 8. Under these conditions, the usable CO 2 in the medium was estimated to be 70,000 μmol. The reactor inlet (10) and outlet (7) were tightly closed with trapped CO 2 gas in contact with water. The photochemical reaction in batch mode was started by starting the irradiation. Gas and liquid samples were collected at regular intervals and analyzed by GC. The reaction was carried out for 20 hours. The temperature of the reaction medium was maintained at 25 ° C. by circulating water (4, 6) through the jacket. The amount of CO 2 consumed to form all types of hydrocarbons and hydrocarbon oxygenates was measured by GC analysis. Therefore, the CO 2 conversion was calculated based on stoichiometry.
実施例2
制御実験
触媒なしでは、および触媒があっても暗中では、反応はみられなかった。触媒が分散された水性アルカリ媒体が窒素でパージされ、飽和され、かつ照射されたとき、非常に少量の炭化水素が、もしかすると触媒表面上の炭素残渣の変換に起因して、最大6時間観察され、その後測定可能な量の生成物を検知することができなかった。しかしながら、CO2でパージおよび飽和すると、炭化水素または炭化水素オキシジェネートの量の増加を、20時間まで、およびそれを超えて観察することができ、その結果、生成物が実際のところCO2の光還元に起因することが確認された。
Example 2
Control experiment No reaction was seen without the catalyst and in the dark even with the catalyst. When the aqueous alkaline medium in which the catalyst is dispersed is purged with nitrogen, saturated and irradiated, very small amounts of hydrocarbons are observed for up to 6 hours, possibly due to the conversion of carbon residues on the catalyst surface. And then no measurable amount of product could be detected. However, when purged and saturated with CO 2 , an increase in the amount of hydrocarbon or hydrocarbon oxygenate can be observed up to 20 hours and beyond so that the product is actually CO 2. It was confirmed that it was caused by photoreduction of.
実施例3
ベース触媒−NaTaO3
NaTaO3が、テフロン(登録商標)で裏打ちされたステンレス鋼オートクレーブ内部に、水20mlに溶解された0.6gのNaOH(0.75M)および0.442gのTa2O5を加えることによって調製された。140℃で12時間の水熱処理の後、沈殿物が収集され、脱イオン水およびエタノールで、最終的には水で数回洗浄され、80℃で5時間乾燥された(X.Li、J.Zang、J.Phys.Chem.C2009、113、19411−19418)。水熱法によって調製されたベース触媒NaTaO3は、図2に示されるような特徴的なXRDパターンを示した。触媒によって示される立方体のモルフォロジーが図4に表され、図5には典型的な電子スペクトルが表され、これは3.88eVのバンドギャップ値を与えた。製品特性と共に実現されたCO2変換が表1に示される。ベース触媒は、CO2光還元に関して穏やかな活性を示した。ベース触媒は、双方の反応、すなわち水素を生成するための水の分解および照射下でのCO2の還元に対して活性であった。
Example 3
Based catalyst -NaTaO 3
NaTaO 3 was prepared by adding 0.6 g NaOH (0.75 M) and 0.442 g Ta 2 O 5 dissolved in 20 ml water inside a Teflon lined stainless steel autoclave. It was. After hydrothermal treatment at 140 ° C. for 12 hours, the precipitate was collected, washed several times with deionized water and ethanol, and finally with water, and dried at 80 ° C. for 5 hours (X. Li, J. et al. Zang, J. Phys. Chem. C2009, 113, 19411-19418). The base catalyst NaTaO 3 prepared by the hydrothermal method showed a characteristic XRD pattern as shown in FIG. The cubic morphology exhibited by the catalyst is represented in FIG. 4, and a typical electronic spectrum is represented in FIG. 5, which gave a band gap value of 3.88 eV. The realized CO 2 conversion with product characteristics is shown in Table 1. The base catalyst showed mild activity for CO 2 photoreduction. The base catalyst was active for both reactions, namely the decomposition of water to produce hydrogen and the reduction of CO 2 under irradiation.
実施例4
ランタナ(La)で修飾されたNaTaO3
La修飾NaTaO3が、オートクレーブ内で、NaOHおよびTa2O5に加えて、0.0065gのLa2O3を添加することによって、上述のものと同じ手順で調製された。熱水処理の後、サンプルは、実施例3に記載されるように、洗浄され、乾燥された。ベース触媒へのランタナの追加は、構造的な変化並びにLaドープ触媒の光物理特性(図5)における変化をもたらす。Laドープの効果が、XRD d−ライン(図3)におけるシフトによって、およびタンタル酸Laに関するバンドギャップの値(純粋なNaTaO3に関して得られる3.88eVに対して、4.1eV)によって明らかとなった。これらの変化は、表1に示されるように、CO2変換の増大をもたらす。ベース触媒と比較して、NaTaO3へのLaの追加が、CO2変換の増大および全ての生成物のなかのメタンおよびメタノールの選択的生成の著しい増大をもたらした。
Example 4
NaTaO 3 modified with lantana (La)
La modified NaTaO 3 was prepared in the same procedure as described above by adding 0.0065 g La 2 O 3 in addition to NaOH and Ta 2 O 5 in an autoclave. After the hydrothermal treatment, the sample was washed and dried as described in Example 3. The addition of Lantana to the base catalyst results in structural changes as well as changes in the photophysical properties of the La doped catalyst (FIG. 5). The effect of La doping is manifested by a shift in the XRD d-line (FIG. 3) and by the band gap value for tantalate La (4.1 eV versus 3.88 eV obtained for pure NaTaO 3 ). It was. These changes result in increased CO 2 conversion, as shown in Table 1. Compared to the base catalyst, the addition of La to NaTaO 3 resulted in increased CO 2 conversion and a significant increase in the selective production of methane and methanol among all products.
実施例5
共触媒としてNiOを有するが、ランタナを持たないNaTaO3
共触媒としてのNiOが、ランタナなしで、タンタル酸ナトリウムに含浸された。CO2光変換における僅かな増加が見られたが、増加の量は、表1に示されるように、La:NaTaO3に関して得られたものと比較して少なかった。
Example 5
NaTaO 3 with NiO as cocatalyst but without lantana
NiO as a cocatalyst was impregnated in sodium tantalate without lantana. A slight increase in CO 2 light conversion was seen, but the amount of increase was small compared to that obtained for La: NaTaO 3 as shown in Table 1.
実施例6
共触媒と共にランタナで修飾されたNaTaO3
共触媒としてのNiO(0.2重量%)が、Ni(NO3)2・6H2Oの水溶液からの湿式含浸、100℃での乾燥、およびその後の空気中270℃での2時間の焼成によって、合成されたNaTaO3:La粉末に担持された。同様に、0.15重量%のPt(H2PtCl6として)および1.0重量%のAu(HAuCl4として)が、湿式含浸によって合成されたNaTaO3:La粉末に担持され、乾燥された。PtおよびAuの塩は、使用前に、各々450℃および200℃で、水素中で還元された。Ag(Ag(NO3)2として)、CuO(Cu(NO3)2・6H2Oとして)、およびRuO2(RuCl3XH2Oとして)が各々1重量%、湿式含浸によってLa:NaTaO3に担持され、乾燥され、300℃で焼成された。
Example 6
NaTaO 3 modified with lantana with cocatalyst
NiO (0.2 wt%) as a cocatalyst is wet impregnated from an aqueous solution of Ni (NO 3 ) 2 .6H 2 O, dried at 100 ° C., and then calcined at 270 ° C. in air for 2 hours Was supported on the synthesized NaTaO 3 : La powder. Similarly, 0.15 weight% of Pt (as
実施例7
共触媒としてのNiOと共にランタナで修飾されたNaTaO3
共触媒としてのNiOがLa修飾NaTaO3に加えられた。LaおよびNiOの両方が存在することによって、表1および図6から理解されるように、2.3%のCO2が変換されるというCO2光還元における実質的な増加がもたらされた。図8に示されるように、NaTaO3とNiOの電子エネルギーレベルにおける非常に有効な相乗効果が、NiO−La:NaTaO3で観察された高活性をもたらす容易な電荷移動を促進した。触媒組成物中での共触媒としてのNiOの使用は、La:NaTaO3と比較して、生成物のうち選択的なメタノールおよびエタノールの生成における急速な増加を意外にももたらす。重要なことに、メタン、エタン、およびアセトアルデヒドに関して著しい相違は観察されなかった。
Example 7
NaTaO 3 modified with lantana with NiO as cocatalyst
NiO as a cocatalyst was added to La-modified NaTaO 3 . The presence of both La and NiO resulted in a substantial increase in CO 2 photoreduction as 2.3% CO 2 was converted, as can be seen from Table 1 and FIG. As shown in FIG. 8, the highly effective synergistic effect on the electronic energy levels of NaTaO 3 and NiO promoted the easy charge transfer resulting in the high activity observed with NiO—La: NaTaO 3 . The use of NiO as a cocatalyst in the catalyst composition surprisingly leads to a rapid increase in the production of selective methanol and ethanol among the products compared to La: NaTaO 3 . Importantly, no significant differences were observed for methane, ethane, and acetaldehyde.
実施例8
共触媒としてのCuOと共にランタナで修飾されたNaTaO3
La:NaTaO3に共触媒としてのCuOを1重量%添加することにより、図5に示されるように、バンドギャップにおいて4.09eVから3.4eVへの有意の減少がもたらされた。NiOのように、CuOもまた電荷移動を促進し、共触媒としてNiOを用いて実現された2.3%に匹敵する、2.1%という高いCO2変換(表1)をもたらす。
Example 8
NaTaO 3 modified with lantana with CuO as cocatalyst
The addition of 1 wt% CuO as a cocatalyst to La: NaTaO 3 resulted in a significant reduction in band gap from 4.09 eV to 3.4 eV, as shown in FIG. Like NiO, CuO also promotes charge transfer, resulting in a high CO 2 conversion (Table 1) of 2.1%, comparable to 2.3% achieved using NiO as a cocatalyst.
実施例9
共触媒としてのPt/Au/AgおよびRuO2と共にランタナで修飾されたNaTaO3
La:NaTaO3と比較して、共触媒としてのPt、Au、Ag、およびRuO2の使用は、CO2変換を改善するが、NiO/CuOほど効果的ではない(表1)。図5によれば、これら4つの共触媒は、La:NaTaO3のバンドギャップを下げ、その結果光吸収を可視領域に拡張する。Auはまた、さらなるプラズモン共鳴吸収を示す。これら4つの共触媒は、電子トラップとして働き、その結果電荷分離を促進する。触媒組成物における共触媒としての白金の使用は、エタノール形成の減少と共にメタン形成の著しい増加をもたらす。これは実に、Au、Ag、またはRuO2のような他の共触媒と比較して予想し得ないことである。
Example 9
NaTaO 3 modified with lanthana with Pt / Au / Ag and RuO 2 as cocatalyst
Compared to La: NaTaO 3 , the use of Pt, Au, Ag, and RuO 2 as cocatalysts improves CO 2 conversion but is not as effective as NiO / CuO (Table 1). According to FIG. 5, these four cocatalysts lower the band gap of La: NaTaO 3 and consequently extend the light absorption to the visible region. Au also exhibits additional plasmon resonance absorption. These four cocatalysts act as electron traps and consequently promote charge separation. The use of platinum as a cocatalyst in the catalyst composition results in a significant increase in methane formation with a decrease in ethanol formation. This indeed, is that not have been predicted by comparing Au, Ag, or with other co-catalysts such as RuO 2.
実施例10
バイメタル共触媒としてのPt−CuおよびPt−Niと共にランタナで修飾されたNaTaO3
全ての触媒に対する生成物の分布は、メタノールおよびエタノールが主な生成物であり、より少ない生成物としてメタン、エタン、およびアセトアルデヒドが存在することを示した。メタンおよびエタンの形成は、Ptの場合に比較的高い。共触媒としてNiOおよびCuOを用いたときに最大の変換が観察されたので、バイメタル共触媒Pt−CuおよびPt−NiがLa:NaTaO3と共に使用された。表1および図7に示される結果は、メタンおよび/またはエタンの形成において有意の増加が存在し、同時に対応するモノメタル共触媒と比べてメタノールの量が多いことを示す。これは、モノメタル共触媒と比較して予期し得ない結果であった。
Example 10
NaTaO 3 modified with lanthana with Pt-Cu and Pt-Ni as a bimetallic cocatalyst
The product distribution for all catalysts indicated that methanol and ethanol were the main products, with fewer products being methane, ethane, and acetaldehyde. The formation of methane and ethane is relatively high with Pt. Bimetallic cocatalysts Pt—Cu and Pt—Ni were used with La: NaTaO 3 since maximum conversion was observed when NiO and CuO were used as cocatalysts. The results shown in Table 1 and FIG. 7 show that there is a significant increase in the formation of methane and / or ethane, and at the same time the amount of methanol is high compared to the corresponding monometal cocatalyst. This was an unexpected result compared to the monometal cocatalyst.
1 Hgランプ源
2 石英窓
3 マグネチックスターラー
4,6 水
7 反応器出口
10 反応器入口
1
Claims (20)
(b)ベース触媒に対して0.5から5重量%の範囲の改質剤、および
(c)ベース触媒に対して0.05から5重量%の範囲の量の少なくとも1つのバイメタル共触媒、
を含み、
前記改質剤が、三酸化ランタン(La2O3)、La、およびこれらの混合物からなる群から選択され、
前記バイメタル共触媒が、Pt、Ag、Au、Cu、Ni、RuO2、CuO、およびNiOからなる群から選択される2つの成分を含む、
二酸化炭素の光触媒還元により低級炭化水素および炭化水素オキシジェネートを製造するための、触媒組成物。 (A) sodium tantalate (NaTaO 3 ) as a base catalyst,
(B) a modifier in the range of 0.5 to 5% by weight relative to the base catalyst, and (c) at least one bimetal cocatalyst in an amount in the range of 0.05 to 5% by weight relative to the base catalyst;
Including
The modifier is selected from the group consisting of lanthanum trioxide (La 2 O 3 ), La, and mixtures thereof;
The bimetallic cocatalyst comprises two components selected from the group consisting of Pt, Ag, Au, Cu, Ni, RuO 2 , CuO, and NiO;
A catalyst composition for producing lower hydrocarbons and hydrocarbon oxygenates by photocatalytic reduction of carbon dioxide.
(b)触媒組成物を得るために、バイメタル共触媒の少なくとも1つの塩でLa2O3/NaTaO3を含浸する段階、
を含む、請求項1に記載の触媒組成物の製造方法。 (A) To obtain La 2 O 3 / NaTaO 3 , tantalum pentoxide (Ta 2 O 5 ), three in an aqueous medium under a hydrothermal condition in a temperature range of 120 to 200 ° C. for 4 to 24 hours. Heating a mixture of lanthanum oxide and NaOH, and (b) impregnating La 2 O 3 / NaTaO 3 with at least one salt of a bimetallic cocatalyst to obtain a catalyst composition;
The manufacturing method of the catalyst composition of Claim 1 containing this.
(b)8〜12の範囲のpHを有する第2の混合物を得るために、第1の混合物に二酸化炭素を通過させる段階、および
(c)低級炭化水素および炭化水素オキシジェネートを生成するために、第2の混合物を300〜700nmの範囲の波長を有する電磁放射に曝す段階、
を含む、低級炭化水素および炭化水素オキシジェネートを製造する方法。 (A) suspending the catalyst composition of claim 1 in aqueous NaOH with stirring in a reactor to obtain a first mixture;
(B) passing carbon dioxide through the first mixture to obtain a second mixture having a pH in the range of 8-12, and (c) to produce lower hydrocarbons and hydrocarbon oxygenates. Exposing the second mixture to electromagnetic radiation having a wavelength in the range of 300-700 nm;
A process for producing lower hydrocarbons and hydrocarbon oxygenates.
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